[COMMUNICATION NO. 1190 FROM
TJ3E
KODAK RESEARCH LABORATORIES]
CERTAIN DERIVATIVES OF sym.-DIMETHYL-pPHENYLENEDIAMINE C. F. H. ALLEN, J. V. CRAWFORD, G. F. FRAME, J. E. JONES, E. R. WEBSTER, AND c. v. WILSON Received A p r i l 18, 19.48
sym.-Dimethyl-p-phenylenediamine(I) can be converted by relatively simple reactions into amines which can be tetrazotized and transformed into azo dyes, and into surface-active substances such as bis-quaternary salts, and bis-acyl derivatives. For instance, it is easily acylated, the nature of the product depending upon the acyl halide selected. Dipalmitoyl and distearoyl derivatives (11; R = Cl&131,CITHB)result when palmitoyl and stearoyl chlorides are used. Of more
roz
1
CHs i O
NO%& CO OCHaCO
CHa -
N
I
-
[CO so2
]ArNOl
COCHzOJ
I11
L
CHa
CHa
I
H A O- N H
'
CHI CHs 0 - N C OI R --+ RCON -
I
I1
interest are the chlorides of nitrated aromatic carboxylic or sulfonic acids, which give rise to nitro derivatives (111),the reduction of which leads to diazotizable amines, and, hence, to azo dyes. The use of the acid chlorides of halogenated aliphatic acids (e.g., chloroacetyl chloride) furnishes a means of preparing bisquaternary salts with bases, some of which have surface-active properties. A variation in the acid chloride is 2,4-dinitrochlorobenzene;selective reduction of the product of the reaction leads to a diamine, which can be used for preparing azo dyes. The following nitrated aromatic acid chlorides have been used: p-nitrobenzoyl-; m- and p-nitrobenzenesulfonyl-; 2-sulfo-4-nitrobenzoyl-; 4-nitrophenoxyacetyl-;and l-nitro-2-naphthoxyacetyl-. The corresponding amines (IV) were prepared by catalytic reduction of the nitro compounds, using Raney nickel. In the general formula, A and B represent the linkages between the aromatic ring, Ar, and the nitrogen of the phenyl-
CHI x-H2NAr-A-k
I
a /
CH3
\ -I!4--B--ArNH~--x
Y
I
Y
IV 666
DERIVATIVES OF DIMETHYL-P-PHENYLENEDIAMINE
667
enediamine, and x is the position of the amino group (y is any other substituent ; unless otherwise indicated, it represents hydrogen). A list of the amines is as follows: V. 1,4-bis-(4’ -Aminobenzoyl-N-methy1amino)benzene; A, B = CO; x = 4; Ar = CJ& VI. 1,4-bis-(3’-Aminobenzenesulfonyl-N-methylamino)benzene; A, B = SO*; x = 3 ; h = CeHr VII, 1 ,4-bis-(4’-Aminobenzenesulfonyl-N-methylamino)benzene; A, B = SO2 ; x = 4;Ar = CeH4 VIIT. 1 ,4-bis-(4’-Amino-2‘-sulfobenzoyl-N-methylamino)benzene; A, B = CO ; x = 4; y = 2 (SOtH); Ar = C6Ha IX. 1,4-bis-(4’-Aminophenoxyacetyl-N-methylamino)benzene;A = OCHaCO; B = COCHzO; x = 4; h = C6H4 X. 1,4-bis-(l’-Amino-2’-naphthoxyacetyl-N-methylamino)benzene; A = OCHZCO; B COCHzO ;x = 1’;Ar = CloHe XI. 1,4-bis-[4‘(or 2’)-Amino-2’(or 4’)-nitrophenyl-N-methylamino]benzene; no A; x = 4’ (or 2’);y = 2’ (or 4’) Azo dyes were subsequently prepared from the bis-diamines and the usual benzene and naphthalene dye intermediates. Those obtained from sulfonic acids dyed wool directly; those from J acid dyed both wool and cotton; while those without sulfonic acid groups colored cellulose acetate. The dyes formed are summarized in Table I, which shows the amine used, the coupling component, and the color of the dyed fabric. Mixed disazo, trisazo, and tetrakisazo dyes were also prepared. The most brillant colors resulted when the aminophenoxyacetyl derivative (IX) was used. The bis-quaternary salt shown in Formula XI1 (X = Cl) was obtained by E=
XI1 treating the sym.-dimethyl-p-phenylenediaminewith two equivalents of chloroacetyl chloride, followed by addition of the bis-halide (11; R = CICH2) thus formed to pyridine. EXPERIMENTAL
Acylation. N , X’-Dimethyl-p-phenylenediaminewas isolated as the solid oxalate; this salt was used in most operations, the free base being liberated by alkali. In some instances when the absence of water was essential, the free base was extracted with ether. N , N’-Distearoyl-N, N’-dimethyl-p-phenylenediamine (11; R = C1,Hrs). To a suspension of 3.2 g. of the oxalate of N,N’-dimethyl-p-phenylenediaminein sodium hydroxide solution (4 g. of the solid dissolved in 50 ml. of water) 6.7 g. of stearoyl chloride was added over a period of one-half hour. The reaction mixture became very viscous. The purplish solid was then triturated with alcohol and separated by filtration. It was twice recrystallized from acetone; the yield was 52%; it melted at 77-79”. N , N’-Dipalmitoyl-N,N’-dimethyl-p-phenylenediamine(11; R = ClbLIm) was similarly prepared in a yield of 73.5%, and recrystallized from pyridine. It melted a t 88-90’.
668
ALLEN, CRAWFORD,
et al.
Anal. Calc'd for C40HnN202: C, 78.4; €I, 11.8. Found: C, 78.5; H, 11.9. TABLE I SYMMETRICAL DISAZODYES W N E usm
COUPLING COXPONENT ON WOOL
V V V V V
1-Hydroxynaphthalene-5-S08H Red-orange 2-Hydroxynaphthalene-7-SOaH Orange Red-orange 1-Hydroxynaphthalene-3,B-diSOsH l-Hydroxynaphthalene-3,8-diSOaH Red-orange Scarlet 2-Hydroxynaphthalene-3,6-diSOtH 2-Hydroxynaphthalene-6,8-diS08H Orange 1,8-Dihydroxynaphthalene-3,6-diSO~H Dull magenta l-Amino-8-hydroxynaphthalene-2,4-diSOaH Magenta l-Amin0-8-hydroxynaphthalene-3~6-diSOsHDull magenta
v V v V V V V V V V V V
VI VI VI VI1 IX IX X XI a
Rose l-Acetamino-8-hydroxynsphthalene-3,6diSOaH 2-Amino-5-hydroxynsphthalene-7-SOaH Orange 2-Beneamido-5-hydroxynaphthalene-7-SO~HRed-orange Maroon 2-Amino-8-hydroxynaphthalene-6-SOaH 2-Amino-8-hydroxynaphthalene-3,6-diSO~HMaroon N-Ethyl-N-8-hydroxyethylaniline N , N-Di-[8-hydroxyethyl] aniline 7-Methyl-l-glyceryl-l , 2,3,4-tetrahydroquinolineb 1-Hydroxynaphthalene-4-S01H Orange l-Amino-8-hydroxynaphthalene-2,4-diSO~HMaroon 5-Hydroxy-1-glycerylaminonaphthaleneb 4-Acetamino-2-gl ycerylaminoanisole 1-Hydroxynaphthalene-4-SOaH
Carmine l-Amino-8-hydroxynaphthalene-2,I-diSOtH Violet l-Amino-8-hydroxynaphthalene-2,4-diSOaH Brown-viole t 5-Hydro~y-l-glycerylaminonaphthalene~
C = cotton; CA = cellulose acetate.
VI IX
Yellow, CA Yellow, CA Red, CA
Violet, CA Salmon, CA
Red-violet, CA
* Glyceryl = 2,3-dihydroxypropyl.
EYPIPICAL POPWJLA
v
Old rose, (3% Red-orange, C
C~ZHPPNIOP C~HSPNIO& CsrHnsN~Oc
CALC'D,
%
14.9 12.6 12.9
14.5 12.6 12.8 _____.__
These two derivatives are softening agents for textiles. Analogous products are mentioned in a patent (1) as being water-repellent, but no examples are given. .V,N'-Dichloroacetyl-N,N'-dimethyl-p-phenylenediamine(11; R CICHn). To a suspension of 31.6 g. of the diamine oxalate in 42.4g. of sodium carbonate and 300 ml. of water waa added gradually 40 g. of chloroacetyl chloride. The mixture was stirred for an addi-
-
DERIV-4TIVES OF DIMETHYL-p-PHENYLENEDIAMJNE
669
tional two hours, and the product separated by filtration. The yield was 30 g. It was recrystallized from acetic acid; thc pink crystals melted a t 190", with decomposition. N,A~'-Di-S'-chloroacetylaminobenzenesuljonyl-~~.~~'-dimethyl-p-phenylened~amzne (IV; A = SOZ,Ar = CsH4, x = 3) was prepared from a solution of 4 g. of the diamine, VI, in 100 ml. of dioxane, to which was added 1 g. of solid sodium carbonate, followed by 5 g. of chloroacetyl chloride, dropwise. The solid product was removed after three hours and recrystdlized from acetic acid. It melted at 184". Anal. Calc'd for C~4HprClzN~OsS2: N, 9.4. Found: N, 9.2. N , AT'-Di-w-carbomethoxyvaleryl-N, N'-dimethyl-p-phenylenediamine [II; R = CHaOCO(CHs),] was prepared from the oxalate as above. It melted at, 73-74'. .4naZ. Calc'd for C Z ~ H ~ ~ C, C 62.9; ~ O ~H,: 7.6; K, 6.7. Found: C, 63.1; H, 7.6; X, 6.6. A',iV'-Di-p-nitrobenzoyl-N,N'-dimethyl-p-phenylenediamine.' To a suspension of 16 g. of h',X'-dimethyl-p-phenylenediamineoxalate and 15.7 g. of sodium carbonate in 200 ml. of water, 29.5 g. of p-nitrobeneoyl chloride was added, with stirring, at room temperature during one-half hour, after which the whole was warmed at 50-60' for three hours. The cooled solution was filtered from the brownish solid, and the latter extracted with 350 ml. of boiling alcohol t o remove p-nitrobenzoic acid. The crude residue (14.2 g.) was recrystdlieed from 200 ml. of glacial acetic acid; the acylated diamine separated as pale yellow needlee; m.p. 256'. I n a similar manner there was prepared .V, N'-di-m-nitrobenzenesulfonyl-N, "-dimethylp-phenjllenediamine; m.p. 215-217", from dioxane or acetic acid, in 6857, yield. It was also obtainerble by using the free base instead of the oxalate, in which case the solution waa allowed t o stand a t room temperature for two days instead of being heated. The paranitro isomer melted above 300". The di-p-nitrophen yacetyl (m.p. 233") and l-amino-2naphthoxyacetyl derivatives (m.p. above 275") were kewise prepared from the oxalate. The 2-sulfo-4-nitrobenzoyl derivative was obtained as follows: The acid chloride of 2-sulfo-4-nitrobenzoieacid was first prepared from 43 g. of thc potassium salt of the acid b y means of 21 g. of thionyl chloride in 300 ml. of pyridine. To this solution was added 15 g. of the free base (prepared from the oxalate by making its aqueous suspension alkaline, shaking, extracting with ether, and removing the solvent) and the mixture stirred on the Rteam-bath for three hours. Upon cooling, 18 g. of the nitro compound separated. The 1,4-bis-(8',4'-dinitrophenyl-A'-methylatnino)benzene was obtaincd by refluxing a mixture of 50 g. of the oxalate, 98.5 g. of 2,4-dinitrochlorobenzene,76 g. of anhydrous sodium acetate, and 400 ml. of alcohol, with stirring, for five hours; the product that separated on cooling was removed and recrystallized from acetic acid, from which it separated in minute red-brown crystals, m.p. 238". All the nitroacyl compounds were reduced t o the corresponding amines catalytically in dcohol in the presence of Raney nickel. The 2.4-dinitrophenyl derivative was reduced selectively, using sodium sulfide, but the location of the amino group wa5 not determined. The melting points of the amines wcre a~ follows: p-aminobenzoyl, 255"; nz-aminobenzenesulfonyl, 218"; p-aminobenzenesulfonyl, 212-226"; p-aminophenoxyacetyl, 207"; 2(0r 4)amino4 (or 2)-nitrophenyl, 221". Analytical figures for representative amines arc collcctv.l in Table 11. Quatarnary salts. The "double-ender" salt (XII; X = C1) was formed very eaaily by merely warming a mixture of pyridine and N,N'-dichloroacet,yl-rS, N'-dimethyl-p-phenylenediamine until the solid was entirely dissolved. I n a few minutes the salt began to separate, and soon the mixture was completely solid. It was triturated with acetone and the salt collected. The salt dissolved readily in methanol and water, but was insoluble in ether and acetone. It has no true melting point; if a specimen in B capillary tube is inserted in a bath, preheated t o about 190", it decomposes at about 195". 1 Dr. Walter A. Gregory assisted in the preparation of large quantities of certain of these interme'diates.
,670
ALLEN, CRAWFORD, et
al.
Anal. Calc'd for C*4H&l*N,02: C1, 15.9. Found: C1, 15.2. The perchlorate (XII; X = ClO,) separated on mixing aqueous solutions of the above chloride and sodium perchlorate. It required several crystallizations from water, using Norit, t o get a colorless product. It decomposed above 220'. bis-Azo dyes from the various diamines (Table I). These were all made in the same general way: (a) Sulfonic acid group present. The diamine (2.5 9.) was dissolved in hot hydrochloric acid (5 ml. of concentrated acid in 25 ml. of water), chilled t o precipitate the salt in a hely-divided condition, and tetrazotized at 5" by sodium nitrite. After fifteen minutes, the solution was added, with stirring, t o 3 g. of 1-naphthol-4-sulfonic acid in 35 ml. of water containing 2.8 g. of sodium hydroxide. The orange dye was salted out after one hour and purified by two re-saltings. (b) No sulfonic acid group. The tetrazotization waa performed in the same manner, and the solution added to a solution of an equivalent amount of the amine, dissolved in 6% hydrochloric acid. Coupling was brought about by adding a strong solution of sodium acetate; when coupling was complete, the dye was precipitated by the addition of aqueous sodium hydroxide. (c) Mixed disazo dye. A representative dye was prepared by coupling the 4'-aminobenzoyldiamine (V) first with 2,4-diaminotoluene in acid solution, and then, after making strongly alkaline, with R salt. It dyes wool orange. (d) Trisazo dye. The 4'-aminophenoxyacetylamine (IX) was tetrazotized and coupled first with m-aminooxanilic acid in weakly acid solution, and then with R salt in alkaline solution. A reddish dye separated; it was collected and dried. It was next diazotized and again coupled with R salt in alkaline solution; the dye slowly separated, was filtered off, and purified by dissolving and salting out with a saturated solution of sodium chloride. It dyes wool a maroon red. (e) Tetrakisazo dye. The diamine (V) was tetrazotized as usual, and coupled in acid solution, pH 4.2, with 2-ethoxy-1-naphthylamine-6-sulfonic acid. The pH was raised first to 5.3 and then t o 6.0, whereupon the dye precipitated. The dried dye was dispersed in very weak alkali, acidified and tetrazotized in the usual manner, and coupled with chromotropic acid in strongly alkaline solution. The brown dye was salted out with saturated salt solution. It dyes wool a dull reddish-brown, which becomes yellow-brown on top-chroming. SUMMARY
sym.-Dimethyl-p-phenylenediamine has been acylated by a variety of acyl halides. The latter included long-chain aliphatic acyl, haloacyl, w-carboalkoxyacyl, nitroarylcarboxy, nitroarylsulfonyl, and nitroaryloxyacyl chlorides, and 2,4-dinitrochlorobenzene. The acyl derivatives were converted, by suitable manipulation, into azo dyes, and quaternary ammonium salts. ROCHESTER 4, NEWYORE REFERENCE (1) AELONY, U. S. Patent 2,342,624 (1944); [Chem. Abstr., 58, 4812 (1944)l.
